Alkoxylate mixtures and detergents containing the same

ABSTRACT

The alkoxylate mixture comprises 0.1 to 99.9% by weight of at least one alkoxylate of the formula (I) 
 
C n H 2n+1 O(A) x (B) y H  (I) 
where A is ethyleneoxy, 
     B is C 3 -C 10 -alkyleneoxy or mixtures thereof, where groups A and B may be present randomly distributed, alternately or in the form of two or more blocks in any order, n is an integer in the range from 8 to 11, x is a number in the range from 1 to 20, y is a number in the range from 0 to 10, and 0.1 to 99.9% by weight of at least one alkoxylate of the formula (II) 
 
C m H 2m+1 O(A) v (B) w H  (II) 
where A is ethyleneoxy,    B is C 3 -C 10 -alkyleneoxy or mixtures thereof, where groups A and B may be present randomly distributed, alternately or in the form of two or more blocks in any order, m is an integer in the range from 12 to 24, v is a number in the range from 1 to 50, w is a number in the range from 0 to 10.

The invention relates to alkoxylate mixtures and to detergentscomprising these, and also to processes for the preparation of thealkoxylate mixtures and to the use of the detergent for the washing orcleaning of textiles.

For the purposes of this invention, detergents are usually used for thewashing of materials of greater or lesser flexibility, preferably thosewhich contain or consist of natural, synthetic or semisynthetic fibermaterials and which consequently have at least partially a textilecharacter.

Detergents of this type have been described widely in the prior art. Avery good review of the mode of action and the composition of detergentsis given, for example, in Ullmann's Encyclopedia of IndustrialChemistry, 5th edition, vol. A8, (1986), pages 315 ff, keyword“Detergents”, and Tai, Formulating Detergents and Personal CareProducts, AOCS Press, 2000. The detergents comprise a surfactant or twoor more surfactants of the same or different surfactant groups andusually further auxiliaries and additives which are either required forformulation and/or which serve to adapt the detergents to the intendedspecific use purpose or the type of application (washing by hand or inmachines). Constituents which can be used in many detergents in additionto the various surfactants in alternating combinations and proportionsare, for example, builders (sequestering agents) and cobuilders, pHregulators, such as inorganic or organic acids, inorganic or organicbases and buffer systems, ion exchangers, dispersants, soil-carryingagents, thickeners, enzymes, bleaching systems, hydrotropic compounds assolubility promoters or solubilizers, such as, for example, urea oralcohols, foam regulators for stabilizing or suppressing foam, skin andcorrosion protectants, disinfecting compoands or systems, for examplethose which comprise iodine or which release chlorine or hypochlorousacid, such as, for example, dichloroisocyanurate, perfume, dyes, optical(fluorescent) brighteners, graying inhibitors, extenders and formulatingagents and disinfecting compoands. An essential part of the cleaningaction of the detergents described in the prior art is due to thesurfactants present therein. Surfactants which are used are ionicsurfactants and, more specifically, both anionic surfactants, such as,for example, alcohol sulfates, alcohol ether sulfates,alkylbenzenesulfonates, α-olefinsulfonates, sulfosuccinates, and alsocationic surfactants, such as, for example, C₈ toC₁₆-dialkyldimethylammonium salts, dialkoxydimethylammonium salts orimidazolinium salts with a long-chain alkyl radical.

The use of amphoteric surfactants, for example of derivatives ofsecondary or tertiary amines, such as, for example, C₆-C₁₈-alkylbetainesor C₆-C₁₅-alkylsulfobetaines or amine oxides, such as alkyldimethylamineoxides, has also already been described.

Nonionic surfactants, in particular also alkoxylates and polyglycosidesof alkanols having, in particular, 8 to 20 carbon atoms, and alkoxylatesof alkylamines and alkylamides are also used in detergents. Inparticular, it is also known to use alkoxylates of oxo alcohols having10 to 13 carbon atoms as surfactants in detergents. DE-A-100 29 692describes such alkoxylates.

In the interest of as sparing a use of materials as possible, goodeconomic feasibility and low impact on the environment, themanufacturers of detergents strive for a continual improvement in theeffectiveness of their products and in particular of the surfactantspresent therein.

It is an object of the present invention to provide alcohol alkoxylatesurfactant systems which, in detergents and cleaners, lead to animproved removal of soil and improve the performance spectrum of thedetergents and cleaners.

We have foand that this object is achieved according to the invention byan alkoxylate mixture comprising

-   0.1 to 99.9% by weight of at least one alkoxylate of the formula (I)    C_(n)H_(2n+1)O(A)_(x)(B)_(y)H  (I)    where-   A is ethyleneoxy,-   B is C₃-C₁₀-alkyleneoxy, preferably propyleneoxy, butyleneoxy,    pentyleneoxy or mixtures thereof,    where groups A and B may be present randomly distributed,    alternately or in the form of two or more blocks in any order,-   n is an integer in the range from 8 to 11,-   x is a number in the range from 1 to 20,-   y is a number in the range from 0 to 10, and    0.1 to 99.9% by weight of at least one alkoxylate of the formula    (II)    C_(m)H_(2m+1)O(A)_(v)(B)_(w)H  (II)    where-   A is ethyleneoxy,-   B is C₃-C₁₀-alkyleneoxy, preferably propyleneoxy, butyleneoxy,    pentyleneoxy or mixtures thereof,    where groups A and B may be present randomly distributed,    alternately or in the form of two or more blocks in any order,-   m is an integer in the range from 12 to 24,-   v is a number in the range from 1 to 50,-   w is a number in the range from 0 to 10.

According to the invention, it has been found that the alkoxylatemixtures derived from shorter-chain and longer-chain alkanols have asignificantly improved washing behavior compared with known systems. Theimprovement is particularly marked compared with the use of exclusivelyshort-chain alkanol ethoxylates. The use of such short-chain alkanolalkoxylates in detergent compositions is known per se.

WO 94/11331 relates to the use of alkoxylates of 2-propylheptanol indetergent compositions for degreasing hard surfaces. The alkoxylateshave 2 to 16 alkylene oxide groups. The majority of the alkylene oxidegroups is preferably in the form of ethylene oxide. According to theexamples, exclusively ethoxylated alcohols are used. It is alsodescribed that the alcohols can be reacted firstly with ethylene oxideand then with propylene oxide. However, no examples or properties aregiven for such alkoxylates. It is stated that the alkoxylates describedexhibit good detergency and wetting action, combined with low foaming.In addition, it is stated that the alkoxylates have a desired thickeningeffect in formulations.

WO 94/11330 relates to alkoxylates of 2-propylheptanol and to the usethereof. The alkoxylates contain 2-propylheptanol which has been reactedfirstly with 1 to 6 mol of propylene oxide and then with 1 to 10 mol ofethylene oxide. According to the examples, a 2-propylheptanol reactedfirstly with 4 mol of propylene oxide and then with 6 mol of ethyleneoxide is used. It is stated that the alkylene oxide adducts exhibit animproved ratio of foaming behavior to detergency. It is also stated thatthe alkoxylates exhibit good wetting behavior. They are used indetergent compositions for the cleaning of textile materials.

U.S. Pat. No. 2,508,036 describes ethoxylates of 2-n-propylheptanol with5 to 15 mol of ethylene oxide. It is stated that the alkoxylates exhibitimproved wetting behavior in aqueous solutions and can therefore be usedin detergents in combination with builders.

The text below describes in more detail the short-chain and thelong-chain alkanol alkoxylate component of the alkoxylate mixturesaccording to the invention.

The mixtures according to the invention comprise 0.1 to 99% by weight,preferably 10 to 90% by weight, in particular 20 to 70% by weight, of atleast one alkoxylate of the formula (I). Accordingly, they comprise 0.1to 99% by weight, preferably 10 to 90% by weight, in particular 30 to80% by weight, of at least one alkoxylate of the formula (II).

In the alkoxylate of the formula (I), A has the meaning ethyleneoxy. Bis preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixturesthereof, preferably propylenenoxy or butyleneoxy, in particularpropyleneoxy.

n is an integer in the range from 8 to 11, n preferably has the value10. These may be linear or branched alkyl radicals, it also beingpossible for mixtures of linear and branched alkyl radicals to bepresent. Particularly preferably, in the alkoxylate of the formula (I)in which n has the value 10, the radical C₁₀H₂₁ has the meaningC₅H₁₁CH(C₃H₇)CH₂. The shorter-chain alkoxylate is thus preferablyderived from 2-propylheptanol, it also being possible for mixtures ofisomers to be present.

For example, in the alkoxylate of the formula (I),

-   -   70 to 99% by weight, preferably 85 to 96% by weight of        alkoxylates A1, in which C₅H₁₁ has the meaning n-C₅H₁₁, and    -   1 to 30% by weight, preferably 4 to 15% by weight of alkoxylates        A2, in which C₅H₁₁ has the meaning C₂H₅CH(CH₃)CH₂ and/or        CH₃CH(CH₃)CH₂CH₂,        may be present in the mixture. Here, C₃H₇ preferably has the        meaning n-C₃H₇.

The preparation of 2-propylheptanol(s) can take place starting fromvaleraldehyde by aldol condensation and subsequent hydrogenation. Thepreparation of valeraldehyde and the corresponding isomers takes placeby hydroformylation of butene, as described, for example, in U.S. Pat.No. 4,287,370; Beilstein E IV 1, 3268, Ullmann's Encyclopedia ofIndustrial Chemistry, 5th edition, volume A1, pages 323 and 328f. Thesubsequent aldol condensation is described, for example, in U.S. Pat.No. 5,434,313. The hydrogenation of the aldol condensation productfollows general hydrogenation conditions.

Furthermore, 2-propylheptanol can be prepared by condensation of1-pentanol (as a mixture of the corresponding 1-methylbutanols) in thepresence of KOH at elevated temperatures, see e.g. Marcel Guerbet, C. R.Acad. Sci., Paris, 128, 511, 1002 (1899). Furthermore, reference is madeto Römpp, Chemie Lexikon, 9th edition, Georg Thieme Verlag, Stuttgart,and the citations given therein, and also to Tetrahedron 1967, Vol. 23,pages 1723-1733.

Suitable singly branched alkyl radicals are also 2-octyl-, 3-octyl-etc., 2-nonyl-, 3-nonyl -etc., 2-decyl-, 3-decyl- etc., 2-undecyl-,3-undecyl- radicals etc. Appropriate alcohols can be prepared byaddition of water to olefins, e.g. α-olefins.

Suitable multiply branched alkyl radicals comprise one or two,preferably one methyl- or ethyl substituent. One example is the(6-ethyl)-2-nonylradical. The appropriate alcohol is accessible byreaction of 2-ethyl hexanal and acetone followed by subsequenthydrogenation.

In the formula (I), x is a number in the range from 1 to 20, preferably3 to 12. y is a number in the range from 0 to 10, preferably 0 to 5,particularly preferably 0. The values of x and y are average valuessince in the alkoxylation of alkanols a distribution of the degree ofalkoxylation is usually obtained. For this reason, it is possible for xand y, like the v and w discussed below, to deviate from whole-numbervalues. The distribution of the degree of alkoxylation can be adjustedto a certain extent through the use of different alkoxylation catalysts.If, in addition to ethylene oxide, one or more longer-chain alkyleneoxides are used for the alkoxylation, then the different alkylene oxideradicals can be present in random distribution, alternately or in theform of two or more blocks in any order. The alkoxylation isparticularly preferably only carried out with ethylene oxide so that apure (poly)ethylene oxide radical is present. The average value of thehomolog distribution is represented by the given numbers x and y.

In the longer-chain alkoxylate of the formula (II), A and B preferablyhave the above meaning. m is an integer in the range from 12 to 24,preferably from 12 to 18, particularly preferably from 12 to 15. Thealkyl radical C_(m)H_(2m+1) may here be linear or branched. It is alsopossible for mixtures of linear and branched alkyl radicals to bepresent. They can originate from any suitable sources. The linearalcohols are of native or synthetic origin. Among the branched alcoholsmention is to be made of the following examples:

-   -   oxo alcohols based on linear or branched olefins,    -   secondary alcohols, obtained for example by paraffin oxidation,    -   alcohols obtained by the SHOP process,    -   alcohols obtainable via GTL technology,    -   alcohols obtainable via Fischer-Tropsch technology,    -   alcohols obtainable via backbone isomerization of the olefins        used for the hydroformylation, in accordance with WO 98/23566.

Appropriate alcohols, which are branched, show the hydroxy group e. g.in 2-, 3-, 4-position. The alkyl radical may be linear or furtherbranched and may show e. g. methyl- or ethyl substituents.

Examples of appropriate alcohols are 2-dodecyl alcohol, 2-tetradecylalcohol, 2-hexadecyl alcohol, in each case accessible by addition ofwater to α-olefins, (7-ethyl)-3-decyl alcohol, respectively(3-methyl-6-ethyl)-2-nonylalcohol, accessible by reaction of 2-ethylhexanal and methyl ethyl ketone followed by subsequent hydrogenation,2-hexadecyl alcohol, respectively 2-octadecyl alcohol, accessible byreaction of C₁₃/C₁₅-aldehyde and acetone, 3-nonadecyl alcohol,respectively (3-methyl)-2-octadecyl alcohol, (3-methyl)-2-hexadecylalcohol, 3-heptadecyl alcohol, accessible by reaction ofC₁₃/C₁₃-aldehyde and methyl ethyl ketone. The reaction products based onC₁₃/C₁₅-aldehyde are branched at about 40-50% in the alpha-position inthe chemical mixtures.

Further examples for appropriate alcohols are linear C₁₂₋₁₄-alkanesshowing a hydroxy group in a non terminal position of the carbon chain,respectively mixtures thereof (e. g. Softanol®-alcohols of NipponShokubai or Tergitol®-alcohols of Dow).

v is a number in the range from 1 to 50, preferably from 3 to 15. b is anumber in the range from 0 to 10, preferably in the range from 0 to 5.In particular, w has the value 0. Reference may be made to the abovestatements regarding x and y in the case of the shorter-chain alcoholalkoxylates.

The invention further provides a process for the preparation ofalkoxylate mixtures as described above, in which alkanols of the formulaC_(n)H_(2n+1)OH and C_(m)H_(2m+1)OH with the given meaning for n and mare reacted with C₂₋₅-alkylene oxides ander alkoxylation conditions andare mixed together before or after alkoxylation or after partialalkoxylation.

The alkoxylation can be carried out, for example, using alkalinecatalysts, such as alkali metal hydroxides or alkali metal alkoxides.The use of these catalysts results in special properties, in particularthe distribution of the degree of alkoxylation.

The alkoxylation can additionally be carried out using Lewis-acidiccatalysis with the special properties resulting therefrom, in particularin the presence of BF₃ x H₃PO₄, BF₃ dietherate, SbCl₅, SnCl₄ x 2 H₂O,hydrotalcite. Suitable as catalyst are also double metal cyanimidecompounds (DMC).

In this process, the excess alcohol can be distilled off, or thealkoxylate can be obtained by a two-stage process. The preparation ofmixed alkoxylates from, for example, EO and PO is also possible, inwhich case firstly a polyethylene oxide block can join to the alkanolradical, followed by an ethylene oxide block, or firstly an ethyleneoxide block and then a propylene oxide block. Random distributions arealso possible. Preferred reaction conditions are given below.

The alkoxylation is preferably catalyzed by strong bases, which areexpediently added in the form of an alkali metal hydroxide or alkalineearth metal hydroxide, usually in an amount of from 0.1 to 1% by weight,based on the amount of the alkanol R²—OH. (Cf. G. Gee et al., J. Chem.Soc. (1961), p. 1345; B. Wojtech, Makromol. Chem. 66, (1966), p. 180.)

An acidic catalysis of the addition reaction is also possible. Inaddition to Bronsted acids, Lewis acids are also suitable, such as, forexample, AlCl₃ or BF₃. (Cf. P. H. Plesch, The Chemistry of CationicPolymerization, Pergamon Press, New York (1963).

In principle, all suitable compounds known to a person skilled in theart may be used as a DMC compound.

DMC compounds suitable as a catalyst are described, for example, in WO99/16775 and in DE 10117273.7. The following are particularly suitableas a catalyst for the alkoxylation of a double metal cyanide compound ofthe formula I:M¹ _(a)[M²(CN)_(b)(A)_(c)]_(d) .fM¹ _(g)X_(n) .h(H₂O).eL.kP  (1),where

-   -   M¹ is at least one metal ion selected from the group consisting        of Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺, Sn²⁺, Pb²⁺, Mo⁴⁺,        Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁺, W⁶⁺, Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺,        Pd²⁺, Pt²⁺, V²⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺,        Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺, Ru²⁺ and Ru³⁺,    -   M² is at least one metal ion selected from the group consisting        of Fe²⁺, Fe³⁺, Co²⁺, Co³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺, Cr²⁺, Cr³⁺,        Rh³⁺, Ru²⁺ and Ir³⁺,    -   A and X, independently of one another, are each an anion        selected from the group consisting of halide, hydroxide,        sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate,        carboxylate, oxalate, nitrate, nitrosyl, hydrogen sulfate,        phosphate, dihydrogen phosphate, hydrogen phosphate and        bicarbonate,    -   L is a water-miscible ligand selected from the group consisting        of alcohols, aldehydes, ketones, ethers, polyethers, esters,        polyesters, polycarbonate, ureas, amides, primary, secondary and        tertiary amines, ligands having pyridine nitrogen, nitriles,        sulfides, phosphides, phosphites, phosphines, phosphonates and        phosphates,    -   k is a fraction or integer greater than or equal to zero and    -   P is an organic additive,    -   a, b, c, d, g and n are selected so that the electroneutrality        of the compound (I) is ensured, it being possible for c to be 0,    -   e is the number of ligand molecules and is a fraction or integer        greater than 0 or 0,    -   f, h and m, independently of one another, are a fraction or        integer greater than 0 or 0.

Examples of organic additives P are: polyether, polyester,polycarbonates, polyalkylene glycol sorbitan ester, polyalkylene glycolglycidyl ether, polyacrylamide, poly(acrylamide-co-acrylic acid),polyacrylic acid, poly(acrylamide-co-maleic acid), polyacrylonitrile,polyalkylene acrylates, polyalkyl methacrylates, polyvinyl methyl ether,polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol,poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid),polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylicacid-co-styrene), oxazoline polymers, polyalkylenimines, maleic acid andmaleic anhydride copolymers, hydroxyethylcellulose, polyacetates, ionicsurface-active and interface-active compounds, gallic acid or salts,esters or amides thereof, carboxylic esters of polyhydric alcohols andglycosides.

These catalysts may be crystalline or amorphous. Where k is zero,crystalline double metal cyanide compounds are preferred. Where k isgreater than zero, crystalline, semicrystalline and substantiallyamorphous catalysts are preferred.

There are various preferred embodiments of the modified catalysts. Apreferred embodiment comprises catalysts of the formula (I) in which kis greater than zero. The preferred catalyst then contains at least onedouble metal cyanide compound, at least one organic ligand and at leastone organic additive P.

In another preferred embodiment, k is zero, e is optionally also zeroand X is exclusively a carboxylate, preferably formate, acetate orpropionate. Such catalysts are described in WO 99/16775. In thisembodiment, crystalline double metal cyanide catalysts are preferred.Furthermore, double metal cyanide catalysts as described in WO 00/74845,which are crystalline or lamellar, are preferred.

The modified catalysts are prepared by combining a metal salt solutionwith a cyanometallate solution, which solution may optionally containboth an organic ligand L and an organic additive P. The organic ligandand optionally the organic additive are then added. In a preferredembodiment of the catalyst preparation, an inactive double metal cyanidephase is first prepared and this is then converted into an active doublemetal cyanide phase by recrystallization, as described inPCT/EP01/01893.

In another preferred embodiment of the catalysts, f, e and k are notzero. These are double metal cyanide catalysts which contain awater-miscible organic ligand (in general in amounts of from 0.5 to 30%by weight) and an organic additive (in general in amounts of from 5 to80% by weight), as described in WO 98/06312. The catalysts can beprepared either with vigorous stirring (24 000 rpm using a Turrax) orwith stirring, as described in U.S. Pat. No. 5,158,922.

Double metal cyanide compounds which contain zinc, cobalt or iron or twothereof are particularly suitable as a catalyst for the alkoxylation.For example, Prussian blue is particularly suitable.

Crystalline DMC compounds are preferably used. In a preferredembodiment, a crystalline DMC compound of the Zn—Co type which containszinc acetate as a further metal salt component is used. Such compoundscrystallize in a monoclinic structure and have a lamellar habit. Suchcompounds are described, for example, in WO 00/74845 or PCT/EP01/01893.

DMC compounds suitable as a catalyst can in principle be prepared by allmethods known to a person skilled in the art. For example, the DMCcompounds can be prepared by direct precipitation, the incipient wetnessmethod, by preparation of a precursor phase and subsequentrecrystallization.

The DMC compounds can be used in the form of a powder, paste orsuspension or can be shaped to give a molding, introduced into moldings,foams or the like or applied to moldings, foams or the like.

The catalyst concentration used for the alkoxylation, based on the finalquantity range, is typically less than 2 000 ppm, preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably lessthan 100 ppm, for example less than 50 ppm.

The addition reaction is carried out at temperatures of from about 90 toabout 240° C., preferably from 120 to 180° C., in a closed vessel. Thealkylene oxide or the mixture of different alkylene oxides is added tothe mixture of alkanol mixture according to the invention and alkaliander the vapor pressure of the alkylene oxide mixture which prevails atthe chosen reaction temperature. If desired, the alkylene oxide can bediluted by up to 30 to 60% with an inert gas. This ensures additionalsafety against explosion-like polyaddition of the alkylene oxide.

If an alkylene oxide mixture is used, then polyether chains are formedin which the various alkylene oxide building blocks are distributed in avirtually random manner. Variations in the distribution of the buildingblocks along the polyether chain arise as a result of different rates ofreaction of the components and can also be achieved voluntarily throughthe continuous introduction of an alkylene oxide mixture ofprogram-controlled composition. If the different alkylene oxides arereacted one after the other, polyether chains are obtained which have ablock-like distribution of the alkylene oxide building blocks.

The length of the polyether chains varies within the reaction productstatistically about an average value which essentially corresponds tothe stoichiometric value which arises from the amount added.

The alkoxylate mixtures according to the invention are preferably usedin detergents or cleaners, where they lead to an improvement in thewashing properties. The invention also provides a detergent or cleanercomprising an alkoxylate mixture as described above. The alkoxylatemixture is here customarily used in an amount of from 0.01 to 80% byweight, preferably in an amount of from 0.01 to 50% by weight, based onthe detergent or cleaner. The detergent or cleaner is preferably usedfor the washing or cleaning of textiles.

The minimum proportion of the alkoxylate mixtures according to theinvention of the overall weight of the detergents according to theinvention is measured so that a significant effect of this additionarises. Good detergency, in particular very good primary detergency, ofthe detergents according to the invention is generally achieved if theproportion of the mixtures in the detergent according to the invention,based on the total weight of the composition, is 0.01 to 50% by weight,preferably 0.1 to 40% by weight, in particular 0.5 to 30% by weight.

For the purposes of this invention, detergents are generally used forthe washing of materials of greater or lesser flexibility, preferablythose which contain or consist of natural, synthetic or semisyntheticfiber materials and which consequently usually have at least partially atextile character. The materials which contain or consist of fibers can,in principle, be in any form which exists in use or for the preparationand processing. For example, fibers may be unarranged in the form ofstaple or aggregate, arranged in the form of threads, yarns, twines, orin the form of fabrics, such as nonwovens, loden materials or felt,wovens, knits in all conceivable types of weave.

These may be raw fibers or fibers in any stages of processing and may benatural protein or cellulose fibers, such as wool, silk, cotton, sisal,hemp, coconut fibers or synthetic fibers, such as, for example,polyester, polyamide or polyacrylonitrile fibers.

The detergents according to the invention can also be used for cleaningfiber-containing materials, such as e.g. backed carpets with cut oruncut pile.

The compositions of the detergents are preferably adapted to thedifferent purposes, as is familiar to the person skilled in the art fromthe prior art. For this purpose, all auxiliaries and additivescorresponding to the purpose and known from the prior art can be addedto the detergents according to the invention.

In addition to the mixtures according to the invention, the followingmay, for example, be present in detergents:

-   -   builders and cobuilders, such as polyphosphates, zeolites,        polycarboxylates, phosphonates or complexing agents    -   ionic surfactants, such as alcohol sulfates/ether sulfates,        alkylbenzenesulfonates, α-olefinsulfonates and other alcohol        sulfates/ether sulfates    -   other nonionic surfactants, such as alkylamine alkoxyates, alkyl        polyglucosides    -   optical brighteners    -   color transfer inhibitors, such as polyvinylpyrrolidone of molar        masses 8000 to 70 000, vinylimidazole/vinylpyrrolidone        copolymers with a molar ratio of the monomers of from 1:10 to        2:1 and molar masses of from 8000 to 70 000, and        poly-4-vinylpyridine N-oxides with molar masses of from 8000 to        70 000    -   extenders, such as sodium sulfate or magnesium sulfate    -   soil release agent    -   incrustation inhibitors    -   bleaching systems, comprising bleach, such as perborate,        percarbonate and bleach activators, such as        tetraacetylethylenediamine, and also bleach stabilizers    -   perfume (oils)    -   foam suppressors, such as silicone oils    -   enzymes, such as amylases, lipases, cellulases, proteases    -   alkali metal donors, such as soluble alkali metal silicates,        e.g. pentasodium methasilicate, sodium carbonate.

Solvents, such as ethanol, isopropanol, 1,2-propylene glycol, butylglycol etc., can, for example, additionally be used in liquiddetergents.

In tablet detergents, it is additionally possible to use tabletingauxiliaries, such as polyethylene glycols with molar masses of more than1000 g/mol, polymer dispersions, and tablet disintegrants, such ascellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinkedpolyacrylates or combinations of acids, such as citric acid and sodiumbicarbonate. A detailed list of possible ingredients is given below.

In some cases, it may be expedient to combine the mixtures usedaccording to the invention with other nonionic surfactants, such asalkylamine alkoxylates, alkylamide alkoxylates, alkyl polyglucosides, orwith ionic, preferably anionic, surfactants, such as, for example,alcohol sulfate/ether sulfates, alkylbenzenesulfonates,α-olefinsulfonates, sulfosuccinates, or with amphoteric surfactants,such as, for example, alkylamine oxides, or betaines.

Examples of surfactants of varying nature suitable for the combinationare given below:

A class of suitable nonionic surfactants are alkylphenol alkoxylates,such as alkylphenol ethoxylates having C₆ to C₁₄-alkyl chains and 5 to30 mol of alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides having 6to 22, preferably 10 to 18, carbon atoms in the alkyl chain. Thesecompoands generally contain 1 to 20, preferably 1.1 to 5, glucosideunits.

Another class of nonionic surfactants are N-alkylglucamides of thestructures

where B¹ is a C₆- to C₂₂-alkyl, B² is hydrogen or C₁- to C₄-alkyl and Dis a polyhydroxyalkyl radical having 5 to 12 carbon atoms and at least 3hydroxyl groups. Preferably, B¹ is C₁₀- to C₁₈-alkyl, B² is CH₃ and D isa C₅- or C₆-radical. For example, such compoands are obtained by theacylation of reductively aminated sugars with acid chlorides of C₁₀- toC₁₈-carboxylic acids.

Further suitable nonionic surfactants are the terminally capped fattyacid amide alkoxylates, known from WO-A 95/11225, of the formulaR¹—CO—NH—(CH₂)_(y)—O—(A¹O)_(x)—R²in which

-   R¹ is a C₅- to C₂₁-alkyl or alkenyl radical,-   R² is a C₁- to C₄-alkyl group,-   A¹ is C₂- to C₄-alkylene,-   y is the number 2 or 3 and-   x has a value from 1 to 6.

Examples of such compoands are the reaction products ofn-butyltriglycolamine of the formula H₂N—(CH₂—CH₂—O)₃—C₄H₉ with methyldodecanoate or the reaction products of ethyltetraglycolamine of theformula H₂N—(CH₂—CH₂—O)₄—C₂H₅ with a standard commercial mixture ofsaturated C₈- to C₁₈-fatty acid methyl esters.

Further suitable nonionic surfactants are also block copolymers ofethylene oxide, propylene oxide and/or butylene oxide (Pluronic® andTetronic® brands from BASF), polyhydroxy or polyalkoxy fatty acidderivatives, such as polyhydroxy fatty acid amides, N-alkoxy- orN-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, inparticular terminally capped ones, and fatty acid alkanolamidealkoxylates.

The additional nonionic surfactants are present in the detergentsaccording to the invention preferably in an amount of from 0.01 to 30%by weight, in particular 0.1 to 25% by weight, especially 0.5 to 20% byweight.

It is also possible to use individual nonionic surfactants or acombination of different nonionic surfactants. The nonionic surfactantsused may come from only one class, in particular only alkoxylated C₈- toC₂₂-alcohols, or surfactant mixtures from different classes can be used.

Suitable anionic surfactants are, for example, fatty alcohol sulfates offatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms,C₁₂-C₁₈-alcohol sulfates, lauryl sulfate, cetyl sulfate, myristylsulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcoholsulfate.

Further suitable anionic surfactants are sulfated ethoxylated C₈- toC₂₂-alcohols (alkyl ether sulfates) or soluble salts thereof. Compoundsof this type are prepared, for example, by firstly alkoxylating a C₈- toC₂₂-, preferably a C₁₀- to C₁₈-alcohol, e.g. a fatty alcohol, and thensulfating the alkoxylation product. For the alkoxylation, preference isgiven to using ethylene oxide, 1 to 50 mol, preferably 1 to 20 mol, ofethylene oxide being used per mole of alcohol. The alkoxylation of thealcohols can, however, also be carried out with propylene oxide on itsown and optionally butylene oxide. Furthermore, also suitable are thosealkylated C₈- to C₂₂-alcohols which contain ethylene oxide and propyleneoxide or ethylene oxide and butylene oxide or ethylene oxide andpropylene oxide and butylene oxide. The alkoxylated C₈- to C₂₂-alcoholscan contain the ethylene oxide, propylene oxide and butylene oxide unitsin the form of blocks or in random distribution. Depending on the natureof the alkoxylation catalyst, alkyl ether sulfates can be obtained witha broad or narrow alkane oxide homolog distribution.

Further suitable anionic surfactants are alkanesulfonates, such as C₈-to C₂₄-, preferably C₁₀- to C₁₈-alkanesulfonates, and soaps, such as,for example, the Na and K salts of saturated and/or unsaturated C₈- toC₂₄-carboxylic acids.

Further suitable anionic surfactants are linear C₈- toC₂₀-alkylbenzenesulfonates (“LAS”), preferably linear C₉- toC₁₃-alkylbenzenesulfonates and -alkyltoluenesulfonates.

Further suitable anionic surfactants are also C₈- toC₂₄-olefinsulfonates and -disulfonates, which may also representmixtures of alklene- and hydroxyalkanesulfonates or -disulfonates, alkylester sulfonates, sulfonated polycarboxylic acids, alkylglycerolsulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycolether sulfates, paraffinsulfonates having about 20 to about 50 carbonatoms (based on paraffin or paraffin mixtures obtained from naturalsources), alkyl phosphates, acyl isethionates, acyl taurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids orhalf-esters or half-amides thereof, alkylsulfosuccinic acids or amidesthereof, mono- and diesters of sulfosuccinic acids, acyl sarcosinates,sulfated alkyl polyglucosides, alkyl polyglycol carboxylates andhydroxyalkyl sarcosinates.

The anionic surfactants are preferably added to the detergent in theform of salts. Suitable cations in these salts are alkali metal ions,such as sodium, potassium and lithium and ammonium salts, such as, e.g.hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium salts.

The anionic surfactants are present in the detergents according to theinvention preferably in an amount of up to 30% by weight, for examplefrom 0.1 to 30% by weight, especially 1 to 25% by weight, in particular3 to 20% by weight. If C₉- to C₂₀ linear alkyl-benzenesulfonates (LAS)are co-used, these are usually employed in an amount up to 15% byweight, in particular up to 10% by weight.

It is possible to use individual anionic surfactants or a combination ofdifferent anionic surfactants. The anionic surfactants used may be fromonly one class, for example only fatty alcohol sulfates or onlyalkylbenzenesulfonates, although it is also possible to use surfactantmixtures from different classes, e.g. a mixture of fatty alcoholsulfates and alkylbenzenesulfonates.

In addition, the surfactant mixtures to be used according to theinvention can be combined with cationic surfactants, customarily in anamount up to 25% by weight, preferably 1 to 15% by weight, for exampleC₈- to C₁₆-dialkyldimethylammonium salts, dialkoxydimethylammonium saltsor imidazolinium salts with a long-chain alkyl radical; and/or withamphoteric surfactants, customarily in an amount up to 15% by weight,preferably 1 to 10% by weight, for example derivatives of secondary ortertiary amines, such as, e.g. C₆-C₁₈-alkylbetaines orC₆-C₁₅-alkylsulfobetaines or alkylamidobetaines or amine oxides, such asalkyldimethylamine oxides.

It is also possible to use cationic surfactants as are described in WO99/19435.

The mixtures to be used according to the invention are usually combinedwith builders (sequestering agents), such as, for example,polyphosphates, polycarboxylates, phosphonates, complexing agents, e.g.methylglycinediacetic acid and salts thereof, nitrilotriacetic acid andsalts thereof, ethylenediaminetetraacetic acid and salts thereof, andoptionally with cobuilders.

Individual builder substances which are highly suitable for thecombination with the mixtures to be used according to the invention maybe listed below:

Suitable inorganic builders are primarily crystalline or amorphousalumosilicates having ion-exchanging properties, such as, in particular,zeolites. Various types of zeolites are suitable, in particular zeolitesA, X, B, P, MAP and HS in their Na form or in forms in which Na ispartially replaced by other cations, such as Li, K, Ca, Mg or ammonium.Suitable zeolites are described, for example, in U.S. Pat. No.4,604,224.

Examples of crystalline silicates which are suitable as builders aredisilicates or phyllosilicates, e.g. δ-Na₂Si₂O₅ or β-Na₂Si₂O₅. Thesilicates can be used in the form of their alkali metal, alkaline earthmetal or ammonium salts, preferably as Na, Li and Mg silicates.Amorphous silicates, such as, for example, sodium metasilicate, whichhas a polymeric structure, or amorphous disilicate can likewise be used.

Suitable carbonate-based inorganic builder substances are carbonates andhydrogencarbonates. These can be used in the form of their alkali metal,alkaline earth metal or ammonium salts. Preference is given to using Na,Li and Mg carbonates or hydrogencarbonates, in particular sodiumcarbonate and/or sodium hydrogencarbonate.

Customary phosphates used as inorganic builders are alkali metalorthophosphates and/or polyphosphates, such as, for example, pentasodiumtriphosphate. Said builder components can be used individually or inmixtures with one another.

In addition, in many cases, it is expedient to add cobuilders to thedetergents according to the invention. Examples of suitable substancesare listed below:

In a preferred embodiment, the detergents according to the inventioncomprise, in addition to the inorganic builders, 0.05 to 20% by weight,in particular 1 to 10% by weight, of organic cobuilders in the form oflow molecular weight, oligomeric or polymeric carboxylic acids, inparticular polycarboxylic acids, or phosphonic acids or salts thereof,in particular Na or K salts.

Low molecular weight carboxylic acids or phosphonic acids suitable asorganic cobuilders are, for example,

phosphonic acids, such as, for example, 1-hydroxyethane-1,1-diphosphonicacid, amino-tris(methylenephosphonic acid),ethylenediaminetetra(methylenephosphonic acid),hexamethylenediaminetetra(methylenephosphonic acid) anddiethylenetriaminepenta-(methylenephosphonic acid);

C₄- to C₂₀-di-, -tri- and -tetracarboxylic acids, such as, for example,succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid,cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acidshaving C₂- to C₁₆-alkyl- or -alkenyl radicals;

C₄- to C₂₀-hydroxycarboxylic acids, such as, for example, malic acid andtartaric acid;

gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrosemono-, di- and tricarboxylic acid;

aminopolycarboxylic acids, such as, for example, nitrilotriacetic acid,β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediaceticacid, isoserinediacetic acid, alkylethylenediaminetriacetates,N,N-bis(carboxymethyl)glutamic acid, ethylenediaminedisuccinic acid andN-(2-hydroxyethyl)iminodiacetic acid, methyl- and ethylglycinediaceticacid.

Examples of oligomeric or polymeric carboxylic acids which are suitableas organic cobuilders are:

oligomaleic acids, as are described, for example, in EP-A 451508 andEP-A 396303;

co- and terpolymers of unsaturated C₄- to C₈-dicarboxylic acids, thecopolymerized comonomers being monoethylenically unsaturated monomersfrom group (i), given below, in amounts of up to 95% by weight, fromgroup (ii) in amounts of up to 60% by weight and from group (iii) inamounts of up to 20% by weight.

Examples of unsaturated C₄- to C₈-dicarboxylic acids in this context aremaleic acid, fumaric acid, itaconic acid and citraconic acid. Preferenceis given to maleic acid.

Group (i) includes monoethylenically unsaturated C₃-C₈-monocarboxylicacids, such as, for example, acrylic acid, methacrylic acid, crotonicacid and vinylacetic acid. From group (i), preference is given to usingacrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C₂- to C₂₂-olefins,vinyl alkyl ethers having C₁- to C₈-alkyl groups, styrene, vinyl estersof C₁- to C₈-carboxylic acids, (meth)acrylamide and vinylpyrrolidone.From group (ii), preference is given to using C₂- to C₆-olefins, vinylalkyl ethers having C₁- to C₄-alkyl groups, vinyl acetate and vinylpropionate.

If the polymers of group (ii) contain copolymerized vinyl esters, someor all of the latter can also be present in hydrolyzed form to givevinyl alcohol structural units. Suitable co- and terpolymers are known,for example, from U.S. Pat. No. 3,887,806 and DE-A 4313909.

Group (iii) includes (meth)acrylic esters of C₁- to C₈-alcohols,(meth)acrylonitrile, (meth)acrylamides of C₁- to C₈-amines,N-vinylformamide and N-vinylimidazole.

Also suitable as organic cobuilders are homopolymers ofmonoethylenically unsaturated C₃-C₈-monocarboxylic acids, such as, forexample, acrylic acid, methacrylic acid, crotonic acid and vinylaceticacid, in particular acrylic acid and methacrylic acid;

copolymers of dicarboxylic acids, such as, for example, copolymers ofmaleic acid and acrylic acid in the weight ratio 10:90 to 95:5,particularly preferably those in the weight ratio 30:70 to 90:10 withmolar masses of from 1000 to 150 000;

terpolymers of maleic acid, acrylic acid and a vinyl ester of aC₁-C₃-carboxylic acid in the weight ratio 10 (maleic acid): 90 (acrylicacid+vinyl ester) to 95 (maleic acid): 10 (acrylic acid+vinyl ester),where the weight ratio of acrylic acid to the vinyl ester can varywithin the range from 30:70 to 70:30;

copolymers of maleic acid with C₂-C₈-olefins in the molar ratio 40:60 to80:20, copolymers of maleic acid with ethylene, propylene or isobutenein the molar ratio 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids onto low molecular weightcarbohydrates or hydrogenated carbohydrates, cf. U.S. Pat. No.5,227,446, DE-A 4415623 and DE-A 4313909, are likewise suitable asorganic cobuilders.

Examples of suitable unsaturated carboxylic acids in this context aremaleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid,methacrylic acid, crotonic acid and vinylacetic acid, and also mixturesof acrylic acid and maleic acid which are grafted on in amounts of from40 to 95% by weight, based on the component to be grafted.

For modification, it is additionally possible for up to 30% by weight,based on the component to be grafted, of further monoethylenicallyunsaturated monomers to be present in copolymerized form. Suitablemodifying monomers are the abovementioned monomers of groups (ii) and(iii).

Suitable graft bases are degraded polysaccharides, such as, for example,acidically or enzymatically degraded starches, inulins or cellulose,protein hydrolyzates and reduced (hydrogenated or reductively aminated)degraded polysaccharides, such as, for example, mannitol, sorbitol,aminosorbitol and N-alkylglucamine, and also polyalkylene glycols withmolar masses up to M_(w)=5000, such as, for example, polyethyleneglycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxideor ethylene oxide/propylene oxide/butylene oxide block copolymers andalkoxylated mono- or polyhydric C₁- to C₂₂-alcohols (cf. U.S. Pat. No.5,756,456).

Polyglyoxylic acids suitable as organic cobuilders are described, forexample, in EP-B-001004, U.S. Pat. No. 5,399,286, DE-A-4106355 andEP-A-656914. The end groups of the polyglyoxylic acids may havedifferent structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acidssuitable as organic cobuilders are known, for example, from EP-A-454126,EP-B-511037, WO-A-94/01486 and EP-A-581452.

In particular, polyaspartic acids or cocondensates of aspartic acid withfurther amino acids, C₄- to C₂₅-mono- or -dicarboxylic acids and/or C₄-to C₂₅-mono- or -diamines are also used as organic cobuilders.Particular preference is given to using polyaspartic acids which havebeen prepared in phosphorus-containing acids and modified with C₆- toC₂₂-mono- or -dicarboxylic acids or with C₆- to C₂₂-mono- or -diamines.

Also suitable as organic cobuilders are iminodisuccinic acid,oxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylates,aminopolyalkylenephosphonates, polyglutamates, hydrophobically modifiedcitric acid, such as, for example, agaric acid, poly-α-hydroxyacrylicacid, N-acylethylenediaminetriacetates, such as lauroylethylenediaminetriacetate and alkylamides of ethylenediaminetetraaceticacid, such as EDTA-tallow amide.

Furthermore, it is also possible to use oxidized starches as organiccobuilders.

Further suitable (co)builders are described in WO 99/19435.

In a further preferred embodiment, the detergents according to theinvention additionally comprise, in particular in addition to theinorganic builders, the anionic surfactants and/or the nonionicsurfactants, 0.5 to 20% by weight, in particular 1 to 10% by weight, ofglycine-N,N-diacetic acid derivatives, as described in WO 97/19159.

It is also frequently expedient to add bleaching systems, consisting ofbleaches, such as, for example, perborate, percarbonate, and optionallybleach activators, such as, for example,tetraacetylethylenediamine,+bleach stabilizers and optionally bleachcatalysts to the detergents according to the invention.

In these cases, the detergents according to the invention additionallycomprise 0.5 to 30% by weight, in particular 5 to 27% by weight,especially 10 to 23% by weight, of bleaches in the form of percarboxylicacids, e.g. diperoxododecanedicarboxylic acid, phthalimidopercaproicacid, or monoperoxophthalic acid or -terephthalic acid, adducts ofhydrogen peroxide with inorganic salts, e.g. sodium perboratemonohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrateor sodium phosphate perhydrate, adducts of hydrogen peroxide withorganic compoands, e.g. urea perhydrate, or of inorganic peroxo salts,e.g. alkali metal persulfates or peroxodisulfates, optionally incombination with 0 to 15% by weight, preferably 0.1 to 15% by weight, inparticular 0.5 to 8% by weight, of bleach activators.

Suitable bleach activators are:

-   polyacylated sugars, e.g. pentaacetylglucose;-   acyloxybenzenesulfonic acids and alkali metal and alkaline earth    metal salts thereof, e.g. sodium p-nonanoyloxybenzenesulfonate or    sodium p-benzoyloxybenzene-sulfonate;-   N,N-diacylated and N,N,N′,N′-tetraacylated amines, e.g.    N,N,N′,N′-tetraacetyl-methylenediamine and -ethylenediamine (TAED),    N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated    hydantoins, such as 1,3-diacetyl-5,5-dimethylhydantoin;-   N-alkyl-N-sulfonylcarbonamides, e.g. N-methyl-N-mesylacetamide or    N-methyl-N-mesylbenzamide;-   N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g.    monoacetylmaleic hydrazide;-   O,N,N-trisubstituted hydroxylamines, e.g.    O-benzoyl-N,N-succinylhydroxylamine,    O-acetyl-N,N-succinylhydroxylamine or O,N,N-triacetylhydroxylamine;-   N,N′-diacylsulfurylamides, e.g.    N,N′-dimethyl-N,N′-diacetylsulfurylamide or    N,N′-diethyl-N,N′-dipropionylsulfurylamide;-   acylated lactams, such as, for example, acetylcaprolactam,    octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam;-   anthranil derivatives, such as, for example, 2-methylanthranil or    2-phenylanthranil;-   triacyl cyanurates, e.g. triacetyl cyanurate or tribenzoyl    cyanurate;-   oxime esters and bisoxime esters, such as, for example,    O-acetylacetone oxime or bisisopropyliminocarbonate;-   carboxylic anhydrides, e.g. acetic anhydride, benzoic anhydride,    m-chlorobenzoic anhydride or phthalic anhydride;-   enol esters, such as, for example, isopropenyl acetate;-   1,3-diacyl-4,5-diacyloxyimidazolines, e.g.    1,3-diacetyl-4,5-diacetoxyimidazoline;-   tetraacetylglycoluril and tetrapropionylglycoluril;-   diacylated 2,5-diketopiperazines, e.g.    1,4-diacetyl-2,5-diketopiperazine;-   ammonium-substituted nitriles, such as, for example,    N-methylmorpholinium acetonitrile methylsulfate;-   acylation products of propylenediurea and    2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea;-   α-acyloxypolyacylmalonamides, e.g.    α-acetoxy-N,N′-diacetylmalonamide;-   diacyldioxohexahydro-1,3,5-triazines, e.g.    1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;-   benz-(4H)1,3-oxazin-4-ones having alkyl radicals, e.g. methyl, or    aromatic radicals, e.g. phenyl, in the 2-position;-   cationic nitriles, as described in DE-A-101 48 577.

The described bleaching system comprising bleaches and bleach activatorscan optionally also comprise bleach catalysts. Examples of suitablebleach catalysts are quaternized imines and sulfonimines, which aredescribed, for example, in U.S. Pat. No. 5,360,569 and EP-A 453 003.Particularly effective bleach catalysts are manganese complexes, whichare described, for example, in WO-A 94/21777. Where used, such compoandsare incorporated into the detergents in amounts of at most up to 1.5% byweight, in particular up to 0.5% by weight, and in the case of veryactive manganese complexes, in amounts up to 0.1% by weight. Furthersuitable bleach catalysts are described in WO 99/19435.

Further bleaching systems based on arylimidoperalkanoic acids which canbe used are described in EP-A-0 325 288 and EP-A-0 490 409.

Bleach Stabilizer

These are additives which are able to absorb, bind or complex traces ofheavy metals. Examples of additives with a bleach-stabilizing actionwhich can be used according to the invention are polyanionic compounds,such as polyphosphates, polycarboxylates, polyhydroxypolycarboxylates,soluble silicates as completely or partially neutralized alkali metal oralkaline earth metal salts, in particular as neutral Na or Mg saltswhich are relatively weak bleach stabilizers. Strong bleach stabilizerswhich can be used according to the invention are, for example,complexing agents, such as ethylenediamine tetraacetate (EDTA),nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA),β-alaninediacetic acid (ADA), ethylenediamine N,N′-disuccinate (EDDS)and phosphonates, such as ethylenediaminetetramethylenephosphonate,diethylenetriaminepentamethylenephosphonate orhydroxyethylidene-1,1-diphosphonic acid in the form of the acids or aspartially or completely neutralized alkali metal salts. The complexingagents are preferably used in the form of their Na salts.

As well as the described bleaching system comprising bleaches, bleachactivators and optionally bleach catalysts, the use of systems withenzymatic peroxide release or of photoactivated bleaching systems isalso possible for the detergents according to the invention, see e.g.U.S. Pat. No. 4,033,718.

For a number of uses, it is expedient for the detergents according tothe invention to comprise enzymes. Enzymes which are preferably used indetergents are proteases, amylases, lipases and cellulases. Preferredamounts of the enzymes are from 0.1 to 1.5% by weight, particularlypreferably 0.2 to 1.0% by weight, of the formulated enzyme. Examples ofsuitable proteases are Savinase and Esperase. A suitable lipase is e.g.Lipolase. A suitable cellulase is e.g. Celluzym. The use of peroxidasesfor activating the bleaching system is also possible. It is possible touse individual enzymes or a combination of different enzymes. Whereappropriate, the detergent according to the invention can also compriseenzyme stabilizers, e.g. calcium propionate, sodium formate or boricacids or salts thereof, and/or antioxidants.

The constituents of detergents are known in principle to the personskilled in the art. The lists, above and below, of suitable constituentsgive merely an illustrative selection of the known suitableconstituents.

In addition to the main components stated hitherto, the detergentsaccording to the invention can also comprise the following furthercustomary additives in the amounts customary for this purpose:

Known dispersants, such as naphthalenesulfonic acid condensates orpolycarboxylates, soil-carrying agents, soil release agents, such aspolyether esters, incrustation inhibitors, pH-regulating compounds, suchas alkalis or alkali donors (NaOH, KOH, pentasodium metasilicate, sodiumcarbonate) or acids (hydrochloric acid, phosphoric acid, amidosulfuricacid, citric acid), buffer systems, such as acetate or phosphate buffer,ion exchangers, perfume, dyes, graying inhibitors, optical (fluorescent)brighteners, color-transfer inhibitors, such as, for example,polyvinylpyrrolidone, biocides, such as isothiazolinones or2-bromo-2-nitro-1,3-propanediol, hydrotropic compoands as solubilitypromoters or solubilizers, such as cumenesulfonates, toluenesulfonates,short-chain fatty acids, urea, alcohols or phosphoric alkyl/aryl esters,foam regulators for stabilizing or suppressing foam, e.g. silicone oils,skin and corrosion protectants, disinfecting compoands or systems, suchas, for example, those which release chlorine or hypochlorous acid, suchas dichloroisocyanurate or which contain iodine, thickeners andextenders and formulating agents.

Graying Inhibitors and Soil Release Polymers

Suitable soil release polymers and/or graying inhibitors for detergentsare for example:

polyesters of polyethylene oxides with ethylene glycol and/or propyleneglycol and aromatic dicarboxylic acids or aromatic and aliphaticdicarboxylic acids;

polyesters of unilaterally terminally capped polyethylene oxides withdi- and/or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from U.S. Pat. No. 3,557,039,GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033and U.S. Pat. No. 5,142,020.

Further suitable soil release polymers are amphiphilic graft orcopolymers of vinyl and/or acrylic esters onto polyalkylene oxides (cf.U.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A-37 11 299, U.S.Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No. 4,849,126)or modified celluloses, such as, for example, methylcellulose,hydroxypropylcellulose or carboxymethylcellulose.

Color Transfer Inhibitors

The color transfer inhibitors used are, for example, homo- andcopolymers of vinylpyrrolidone, of vinylimidazole, of vinyloxazolidoneand of 4-vinylpyridine N-oxide having molar masses of from 15 000 to 100000, and crosslinked finely divided polymers based on these monomers.The use mentioned here of such polymers is known, cf. DE-B-22 32 353,DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.

Suitable polyvinylpyridinebetaines are described, for example in Tai,Formulating Detergents and Personal Care Products, AOCS Press, 2000,page 113.

In addition to the use in detergents and cleaners for domestic textilewashing, the detergent compositions which can be used according to theinvention can also be used in the field of commercial textile washingand of commercial cleaning. In this field of use, peracetic acid isusually used as bleach, and is added to the wash liquor as an aqueoussolution.

Use in Textile Detergents

A typical pulverulent or granular heavy-duty detergent according to theinvention may, for example, have the following composition:

-   -   0.5 to 50% by weight, preferably 5 to 30% by weight, of at least        one anionic and/or nonionic surfactant, including the mixtures        according to the invention,    -   0.5 to 60% by weight, preferably 15 to 40% by weight, of at        least one inorganic builder,    -   0 to 20% by weight, preferably 0.5 to 8% by weight, of at least        one organic cobuilder,    -   2 to 35% by weight, preferably 5 to 30% by weight, of an        inorganic bleach,    -   0.1 to 20% by weight, preferably 0.5 to 10% by weight, of a        bleach activator, optionally in a mixture with further bleach        activators,    -   0 to 1% by weight, preferably up to at most 0.5% by weight, of a        bleach catalyst,    -   0 to 5% by weight, preferably 0 to 2.5%, of a polymeric color        transfer inhibitor,    -   0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of        protease,    -   0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of        lipase,    -   0 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of a soil        release polymer,        ad 100% of customary auxiliaries and adjuncts and water.

Inorganic builders preferably used in detergents are sodium carbonate,sodium hydrogencarbonate, zeolite A and P, and amorphous and crystallineNa silicates, and also phyllosilicates.

Organic cobuilders preferably used in detergents are acrylic acid/maleicacid copolymers, acrylic acid/maleic acid/vinyl ester terpolymers andcitric acid.

Inorganic bleaches preferably used in detergents are sodium perborateand sodium carbonate perhydrate.

Anionic surfactants preferably used in detergents are linear andslightly branched alkylbenzenesulfonates (LAS), fatty alcoholsulfates/ether sulfates and soaps.

Enzymes preferably used in detergents are protease, lipase, amylase andcellulase. For the commercially available enzymes, amounts of from 0.05to 2.0% by weight, preferably 0.2 to 1.5% by weight, of the formulatedenzyme, are generally added to the detergent. Suitable proteases are,for example, Savinase, Desazym and Esperase. A suitable lipase is, forexample, Lipolase. A suitable cellulase is, for example, Celluzym.

Soil release polymers and graying inhibitors preferably used indetergents are graft polymers of vinyl acetate onto polyethylene oxideof molar mass 2500-8000 in the weight ratio 1.2:1 to 3.0:1, polyethyleneterephthalates/oxyethylene terephthalates of molar mass 3000 to 25 000from polyethylene oxides of molar mass 750 to 5000 with terephthalicacid and ethylene oxide and a molar ratio of polyethylene terephthalateto polyoxyethylene terephthalate of from 8:1 to 1: 1, and blockpolycondensates according to DE-A-44 03 866.

Color transfer inhibitors preferably used in detergents are soluble NVPhomopolymers and/or vinylpyrrolidone and vinylimidazole copolymers withmolar masses greater than 5000.

The detergents are often in solid, pulverulent form, in which case theyusually additionally comprise customary extenders, which give them goodflowability, dosability and solubility and which prevent caking anddusting, such as sodium sulfate or magnesium sulfate.

The pulverulent or granular detergents according to the invention cancomprise up to 60% by weight of inorganic extenders. However, thedetergents according to the invention preferably have a low content ofextenders and comprise only up to 20% by weight, particularly preferablyonly up to 8% by weight, of extenders.

The detergents according to the invention can have various bulkdensities in the range from 300 to 1200, in particular 500 to 950 g/l.Modern compact detergents usually have high bulk densities and aregranular in structure. Compact or ultracompact detergents and extrudateshave a bulk density of >600 g/l. These are becoming more important.

If they are to be used in liquid form, they may be in the form ofaqueous microemulsions, emulsions or solutions. In liquid detergents,solvents such as ethanol, isopropanol, 1,2-propylene glycol or butylglycol can additionally be used.

In the case of gel detergents according to the invention, thickeners,such as, for example, polysaccharides and/or weakly crosslinkedpolycarboxylates (for example Carbopol® from Goodrich) can additionallybe used.

In the case of tablet detergents, tableting auxiliaries, such as, forexample, polyethylene glycols with molar masses of >1000 g/mol, polymerdispersions, and tablet disintegrants such as cellulose derivatives,crosslinked polyvinylpyrrolidone, crosslinked polyacrylates orcombinations of acids, e.g. citric acid+sodium bicarbonate, to. name buta few, are additionally required.

The present invention further provides for the use of the mixtures inthe preparation of detergents.

The invention further provides a washing process using a detergentaccording to the invention.

The invention is described in more detail by reference to the examplesbelow.

PREPARATION EXAMPLES

The alcohol and KOH (finely powdered) are mixed and dewatered at 80° C.and 40 mbar for 1 hour. The reaction product is placed into anautoclave, the autoclave is rendered inert by flushing twice withnitrogen and is then heated to 120° C. Over the course of 15 minutes,ethylene oxide is metered in to a maximum pressure of 1 bar. Thispressure is held for 5 min, then increased by adding ethylene oxide overthe course of 60 min to 3 bar, this pressure is held for 5 hours and,finally, the pressure is increased to 6 bar. In the case of the lastmetered addition, only enough ethylene oxide is added until the amountof ethylene oxide given below is reached. The pressure is then held at 6bar through the metered addition of nitrogen. After a reaction time of afurther 10 hours, the system is left to cool to room temperature and thereaction product is removed. Volatile components are removed on a rotaryevaporator at 30 mbar and 80° C.

Example 1 2-Propylheptanol+5 EO

474 g of 2-propylheptanol (3.0 mol), 661 g of ethylene oxide (15.0 mol)and 2.3 g of KOH were used.

Example 2 2-Propylheptanol+7 EO

474 g of 2-propylheptanol (3.0 mol), 925 g of ethylene oxide (21.0 mol)and 2.8 g of KOH were used.

Example 3 2-Propylheptanol+10 EO

474 g of 2-propylheptanol (3.0 mol), 1322 g of ethylene oxide (30.0 mol)and 3.6 g of KOH were used.

Example 4 iso-C13-Alcohol 5 EO

401 g of iso-C13-alcohol (2.0 mol), 441 g of ethylene oxide (10.0 mol)and 1.7 g of KOH were used.

Example 5 iso-C13-Alcohol 7 EO

401 g of iso-C13-alcohol (2.0 mol), 617 g of ethylene oxide (14.0 mol)and 2.0 g of KOH were used.

Example 6 iso-C13-Alcohol 11 EO

401 g of iso-C13-alcohol (2.0 mol), 969 g of ethylene oxide (22.0 mol)and 2.7 g of KOH were used.

Application Examples

Washing conditions Primary detergency Machine Launder-o-meter fromAtlas, Chicago USA Wash liquor 250 ml Wash time 30 min. at the giventemperature (including heating time) Detergent dose 4.5 g/l Waterhardness 3 mmol/l  Ca:Mg 4:1 Liquor ratio 1:12.5 Test fabricManufacturer wfk 10C wool grease/ wfk Testgewebe GmbH, pigment on cottonBruggen, Germany wfk 10D skin grease/ wfk Testgewebe GmbH, pigment oncotton Bruggen, Germany wfk 20D skin grease/ wfk Testgewebe GmbH,pigment on mixed fabric Bruggen, Germany wfk 10PF vegetable fat/ wfkTestgewebe GmbH, pigment on cotton Bruggen, Germany EMPA 101 olive oil/EMPA Test materials, St. soot on cotton Gallen, Switzerland

The washed test fabrics are measured using a photometer from Datacolor(Elrepho 2000). The soil removal is given as a percentage. The higherthe soil removal, the better the primary detergency. Washing formulationSodium carbonate   12% Sodium perborate monohydrate 14.4% Sodiumsilicate   3% Sodium sulfate   4% Soap  0.5% AA/MA copolymer 7:3   5%TAED   4% Carboxymethylcellulose  1.2% Zeolite A   30% Surfactantsaccording to the invention as given Water ad 100%R = reflectance value at 460 nm

The results of the washing experiments are summarized in the tablebelow. TABLE Amount Amount Fabric type wfk 10 PF EMPA Surfactant 1Surfactant 2 of of wfk 10C wfk 10D wfk 20 D Soil 101 Soil From fromsurfactant 1 surfactant 2 Wash Soil removal Soil removal Soil removalremoval removal Example Example [%] [%] temperature in % in % in % in %in % 1 — 6 — 25° C. 5.2 0.4 4.0 — — 1 4 3 3 25° C. — 19.9 26.2 — — 1 5 33 25° C. 7.7 20.4 22.5 — — 1 — 6 — 40° C. 6.1 0.4 3.5 6.9 3.3 1 4 3 340° C. 23.2 29.5 32.5 26.3 7.7 1 5 3 3 40° C. 17.6 24.6 30.8 — 11.1 1 64 2 40° C. 25.0 30.6 31.1 28.7 6.3 1 — 6 — 60° C. 13.1 0.7 5.9 13.8 7.51 4 3 3 60° C. 40.8 48.9 27.7 29.4 — 1 5 3 3 60° C. 28.1 32.2 59.5 —11.3 1 6 4 2 60° C. 23.4 40.8 31.7 40.1 16.9 2 — 6 — 40° C. 4.9 26.010.3 5.7 9.2 2 4 3 3 40° C. 15.8 46.1 21.5 11.8 12.2 2 5 3 3 40° C. 19.437.9 36.8 18.6 15.1 2 — 6 — 60° C. 17.9 32.0 7.7 6.9 10.7 2 4 3 3 60° C.29.9 40.8 18.5 18.8 11.6 2 5 3 3 60° C. 25.6 46.6 40.0 26.4 17.4 3 — 6 —40° C. 7.6 2.1 1.9 7.5 7.0 3 4 3 3 40° C. 15.5 19.2 16.4 — 10.8 3 5 3 340° C. 19.4 37.8 41.7 31.6 8.1 3 — 6 — 60° C. 14.7 0.3 7.2 13.5 10.8 3 43 3 60° C. 28.5 18.8 35.6 — 21.2 3 5 3 3 60° C. 25.3 40.1 34.5 30.0 17.2

As the results summarized in the table show, the use of the alkoxylatemixture according to the invention leads to a considerable improvementin the primary detergency in the detergent.

Example 7 Catalyst Preparation: DMC-Catalyst

In a stirrid tank having a volume of 30 l, equipped a mechanicalstirrer, dip pipe for metering, pH-probe head and scattered light probehead, 16000 g aqueous hexa cyano cobaltato acid (cobalt content: 9 g (l)were provided and heated to 50° C. under agitation. Afterwards 9224 g ofan aqueous solution of zinc acetate dihydrate (zinc content: 2,6% byweight), which was tempered to 50° C., too, were added under agitationwith an agitation power of 0.4 W/l within 15 minutes.

351 g Pluronic® PE 6200 (BASF AG) were added to this precipitationsuspension and the mixture is stirred for additional 10 minutes.

Afterwards additional 3690 g of an aqueous solution of zinc acetatedihydrate (zinc content: 2.6% by weight) were added under agitation withan agitation power of 1 W/l within 5 minutes.

The suspension was stirred for two hours. The pH-value dropped duringthis time from 4.02 to 3.27 and remained constant. The obtainedprecipitation suspension was filtered off afterwards and the solidresidue was washed with six times the amount of water.

The wet solid residue was dried and was dispersed in Tridekanol® using amill (Spalt-Rotor-Mühle). The obtained suspension has a content ofmultimetall cyanide of 5% by weight.

2-Propylheptyl alcohol+5 EO, 25 ppm DMC

474 g (3.0 mol) 2-propyl-heptyl alcohol-1 (isomeric mixture of 87% of2-propyl-heptyl alcohol-1, 11% of 2-propyl-4-methyl heseyl alcohol-1,<1% 2-propyl-5-methyl hexyl alcohol-1) and 0.567 g of a suspension ofdouble metal cyanide with a content of 5% in an isomeric mixture of2-propyl heptyl alcohol (25 ppm in respect of the product) as catalystwere dehydrated at a temperature of 80° C. and at about 1 mbar, added toa 2 1-autoclave, flushed three times with nitrogen and heated to 120° C.afterwards. After reaching this temperature 660 g (15 mol) ethylenoxidewere added continuously at a pressure of 0.1 to 3.7 bar (gradient ofpressure 6 bar/90 min). After completion of the addition of the oxidethe reaction mixture was left to react (20 minutes), was cooled to 80°C. afterwards, flushed three times with nitrogen and emptied. Theobtained product was degassed at 80° C. under reduced pressure (<30mbar) at the rotary evaporator (reaction product has not been filtered).

Example 8

2-Propylheptyl Alcohol+8 EO, 25 ppm DMC

Reaction was conducted with 474 g (3.0 mol) 2-propylheptyl alcoholisomeric mixture, 0.77 g of a suspension of double metalcyanide and 1060g (24.0 mol) ethylene oxide. The products obtained according to examples7 and 8 were tested according to the products obtained according toexamples 1 to 6.

1-10. (canceled)
 11. An alkoxylate mixture, comprising: 10 to 90%, byweight, of at least one alkoxylate of the formula (I)C₅H₁₁CH(C₃H₇)CH₂O(A)_(x)H  (I) wherein A is ethyleneoxy, x is a numberin the range from 1 to 20, and 10 to 90%, by weight, of at least onealkoxylate of the formula (II)C_(m)H_(2m+1)O(A)_(v)(B)_(w)H  (II) wherein A is ethyleneoxy, B isC₃-C₁₀-alkyleneoxy or mixtures thereof, wherein groups A and B may bepresent, randomly distributed, alternately, or in the form of two ormore blocks, in any order, m is an integer in the range from 12 to 24, vis a number in the range from 1 to 50, w is a number in the range from 0to
 10. 12. The mixture as claimed in claim 1, wherein, in the alkoxylateof the formula (I), 70 to 99%, by weight, of alkoxylates A1, in whichC₅H₁₁ has the meaning n-C₅H₁₁, and 1 to 30%, by weight, of alkoxylatesA2, in which C₅H₁₁ has the meaning C₂H₅CH(CH₃)CH₂ and/orCH₃CH(CH₃)CH₂CH₂, are present in the mixture.
 13. The mixture as claimedin claim 11, wherein, in the alkoxylate of the formula (II), m is aninteger in the range from 12 to
 18. 14. The mixture as claimed in claim11, wherein, in the alkoxylate of the formula (I), x is a number in therange from 3 to 12, and in the general formula (II), v is a number inthe range from 3 to 15, and w has the value
 0. 15. A process for thepreparation of the alkoxylate mixture, as claimed in claim 11,comprising, reacting alkanols of the formula C_(m)H_(2m+1)OH and2-propyl heptyl alcohol, with the given meaning for m, withC₂₋₅-alkylene oxides, under alkoxylation conditions, and mixing themtogether, before, or after, alkoxylation, or after partial alkoxylation,and wherein the alkoxylation may be conducted in the presence of adouble metal cyanide compound as catalyst.
 16. A detergent or cleanercomprising the alkoxylate mixture as claimed in claim 11, and one ormore additives.
 17. A detergent or cleaner, comprising the alkoxylatemixture, as claimed in claim 11, wherein the alkoxylate mixture ispresent in an amount from 0.01 to 80%, by weight, based on the detergentor cleaner.
 18. A method of washing or cleaning textiles, comprisingapplying the detergent or cleaner, as claimed in claim 16, to one ormore textiles.